Potassium Carbonate → 5-(2-tert-Butoxycarbonyl-vinyl)-2-[(4-methoxy-benzenesulfonyl)-methyl-amino]-3-methyl-benzoic acid methyl ester

HRID 583353Notes

Reaction equation

HRID 583353 reaction equation
[CH3:1][O:2][C:3](=[O:25])[C:4]1[CH:9]=[C:8](Br)[CH:7]=[C:6]([CH3:11])[C:5]=1[N:12]([S:14]([C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=1)(=[O:16])=[O:15])[CH3:13].[C:26]([O:30][C:31](=[O:34])[CH:32]=[CH2:33])([CH3:29])([CH3:28])[CH3:27].[Br-].C([NH3+])(C)(C)C.C([O-])([O-])=O.[K+].[K+]>CN(C=O)C.C([O-])(=O)C.C([O-])(=O)C.[Pd+2].O>[CH3:1][O:2][C:3](=[O:25])[C:4]1[CH:9]=[C:8]([CH:33]=[CH:32][C:31]([O:30][C:26]([CH3:29])([CH3:28])[CH3:27])=[O:34])[CH:7]=[C:6]([CH3:11])[C:5]=1[N:12]([S:14]([C:17]1[CH:22]=[CH:21][C:20]([O:23][CH3:24])=[CH:19][CH:18]=1)(=[O:16])=[O:15])[CH3:13]

Participants

8

Reactant 4

HCID 11430Potassium CarbonateHCID 15458tert-Butyl acrylateHCID 21584498Tert-butyl ammonium bromideHCID 699040625-Bromo-2-[(4-methoxy-benzenesulfonyl)-methyl-amino]-3-methyl-benzoic acid methyl ester

Product 1

HCID 700548965-(2-tert-Butoxycarbonyl-vinyl)-2-[(4-methoxy-benzenesulfonyl)-methyl-amino]-3-methyl-benzoic acid methyl esterYield 88.3%

Reagents, catalysts & solvents 3

HCID 167845palladium(II) acetateCatalystHCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

A mixture of 1.28 g (3.0 mmol) of the product of Example 202, 1.31 ml (9.0 mmol) of t-butylacrylate, 33.75 mg (0.15 mmol) of palladium diacetate, 1.0 g (3.15 mmol) of t-butyl ammonium bromide and 1.24 g (9.0 mmol) of K2CO3 in 10 ml of DMF was stifled at 85° C. for 6 h. The reaction mixture was poured into water and extracted with ethyl acetate. The combined organics were washed with water and brine, dried over MgSO4, filtered and concentrated in vacuo. The resulting residue was dissolved in 20 ml of dichloromethane and stired with 1.0 g of celite and 1.0 g of silica gel for 20 min, filtered and concentnted in vacuo. The resulting residue was chromatographed on silica gel eluting with ETOAc/Hexane (1:5) to provide 1.26 g (88%) of the desired product as a white solid. Electrospray Mass Spec 476(M+H).

Workup

  1. extractionextracted with ethyl acetate
  2. washThe combined organics were washed with water and brine
  3. dry with materialdried over MgSO4
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. dissolutionThe resulting residue was dissolved in 20 ml of dichloromethane
  7. waitstired with 1.0 g of celite and 1.0 g of silica gel for 20 min
  8. filtrationfiltered
  9. customThe resulting residue was chromatographed on silica gel eluting with ETOAc/Hexane (1:5)

Sources & evidence

ORD record
ord-25cc740672584eff84def69d76f51ab0
Source dataset
uspto-grants-1999_07
Patent number
US05929097

Reaction notes

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